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Chapter 6

Here are the key steps and results from the example: - The reaction is: C2H2 + H2 ⇌ C2H4 - At 1120°C and 1 bar, Kc = 0.1591 - For an equimolar feed of C2H2 and H2, the equilibrium mole fractions are: xC2H2 = 0.3939 xC2H4 = 0.6061 xH2 = 0.3939 So the composition of the product stream at equilibrium is: 39.39% C2H2, 60.61% C2H4, 39.39% H2

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Victor M. Jaki
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127 views

Chapter 6

Here are the key steps and results from the example: - The reaction is: C2H2 + H2 ⇌ C2H4 - At 1120°C and 1 bar, Kc = 0.1591 - For an equimolar feed of C2H2 and H2, the equilibrium mole fractions are: xC2H2 = 0.3939 xC2H4 = 0.6061 xH2 = 0.3939 So the composition of the product stream at equilibrium is: 39.39% C2H2, 60.61% C2H4, 39.39% H2

Uploaded by

Victor M. Jaki
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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CHAPTER 6

CHEMICAL-REACTION
EQUILIBRIA
6.1 The Reaction Coordinate

The general chemical reaction :

where | vi | is a stoichiometric coefficient and Ai


stands for a chemical formula.
For vi :
Positive ( + ) for product Negative ( - ) for
reactants
6.1 The Reaction Coordinate

Example :
CH4 + H2O CO + 3H2

The stoichiometric numbers are:

The stoichiometric number for an inert species is


zero
6.1 The Reaction Coordinate

Since
dni = vi d ( i = 1 , 2 ,.N)

is called the reaction coordinate, it characterizes the


extent or degree to which a reaction has taken place.

or (i = 1,2, N)
6.1 The Reaction Coordinate

Sum over all species

or

where
Example (page 486)
Consider a vessel which initially contains only no
mol of water vapor. If decomposition occurs
according to the reaction,
H2O H2+ 0.5 O2

find expressions which relate the number of moles


and the mole fraction of each chemical species to the
reaction coordinate e.
Example (page 486)

Solution

Application of equation (13.4) and (13.5) yields


Example (page 486)

The fractional decomposition of water vapor is:

when n0=1, is directly related to the fractional


decomposition of the water vapor.
Multireaction Stoichiometry

When two reactions occur simultaneously


(i = 1, 2, N)
Integration from ni0 and 0 to ni and j yields
(i = 1, 2, N)
Summing over all species yields
Multireaction Stoichiometry

The definition of a total stoichiometric number for


a single reaction has its counterpart in the definition
,
Combining with equation (13.6) gives the mole
fraction
(i = 1, 2, N)
6.2 APPLICATION OF EQUILIBRIUM
CRITERIA TO CHEMICAL REACTIONS
At the equilibrium state:
( dGt )T , P = 0
The total Gibbs energy Gt is at minimum
Its differential = 0
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT

The fundamental property relation for single-phase


systems, provides an expression for the total
differential of the Gibbs energy:
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT

If changes in mole numbers ni occur as the result of a


single chemical reaction in a closed system , then
each dni may be replaced by the product vi d .
6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT

Since nG is a state function , the right side of this


equation is an exact differential expression:

For chemical-reaction equilibrium:


6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT

Recall the definition of the fugacity of a species


in solution:

For a pure species i in its standard start at the same


temperature :

6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT

The difference between both equations is


6.3 THE STANDARD GIBBS-ENERGY
CHANGE AND THE EQUILIBRIUM
CONSTANT

Also, by definition

K is a function of only temperature

In spite of its dependence on temperature , K is


called the equilibrium constant for the reaction; ,
represented by G , is called the standard Gibbs-
energy change of reaction.
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT

The dependence of G on T :

which can be re-written as

The equation gives the effect of temperature on


equilibrium constant and hence on the equilibrium
conversion.
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT

When H
negative = exothermic reaction
positive = endothermic reaction

If H is assumed independent of T, then:

a plot of ln K versus the reciprocal of absolute


temperature is a straight line.
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT

The rigorous development of the effect of


temperature on the equilibrium constant is based on
the definition of the Gibbs energy , written for a
chemical species in its standard state:

Multiplication by vi and summation over all species


gives:

6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT

As a result of the definition of standard property


change of reaction, this reduces to:

where the standard heat of reaction and standard


entropy change is related to temperature:
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT

However,

so,

and,
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT

The preceding equation may be reorganized so as to


factor K into three terms , each representing a basic
contribution to its value :
K = K0 K1 K2
6.4 EFFECT OF TEMPERATURE ON
THE EQUILIBRIUM CONSTANT

K0 represents the equilibrium constant at reference


temperature T0 :
6.5 EVALUATION OF EQUILIBRIUM
CONSTANTS
Values of Go for many reactions are tabulated

No way to measure Gof experimentally

Gof are calculated using equation


Example (page 496)

Calculate the equilibrium constant for the vapor-


phase hydration of ethylene at 145 and at 320C from
data given in Appendix C.

Solution
First determine values for A, B, C, and D for
the reaction
Example (page 496)

The meaning of is indicated by: A = (C2H5 OH) -


(C2H4) - (H2O). Thus, from the heat-capacity data of
Table C. 1:

A = 3.518 - 1.424 - 3.470 = - 1.376

B = (20.001 - 14.394 - 1.450) x 10-3 = 4.157 x l0-3

C = (-6.002 + 4.392 - 0.000) x 10-6 = -1.610 x 10-6

D = (-0.000 - 0.000 - 0.121) x 105 = -0.121 x 105


Example (page 496)

Values of H298 and G298 at 298.15K for the


hydration reaction are found from the heat-of-
formation and Gibbs-energy-of-formation data of
Table C.4:
H298 = -235,100 - 52,510 - (-241,818) = -45,792 J/mol

G298 = -168,490 - 68,460 - (-228,572) -8,378 J/mol


Example (page 496)

For T = 145 + 273.15 = 418.15 K, values of the


integrals in Eq. (13.18) are:

IDCPH(298.15,418.15;-1.376,4.157E-3,-1.610E-6,-
0.121 E+5) = -23.121

IDCPS(298.15,418.15;-1.376,4.157E-3,-1.610E-6,-
0.121 E+5) = -0.06924
Example (page 496)
Substitution of values into Eq. for a reference
temperature of 298.15 gives:
G418

8,378 45,792 45,792 23.121
0.06924 1.9356
RT 8.314 298.15 8.314 418.15 418.15
For T = 320 + 273.15 = 593.15 K,
IDCPH(298.15,593.15;-1.376,4.157E-3,-1.610E-6,-
0.121 E+5) = 22.632
IDCPS(298.15,593.15;-1.376,4.157E-3,-1.610E-6,-0.121
E+5) = 0.01731
So,
G593

8,378 45,792 45,792 22.632
0.01731 5.8286
RT 8.314 298.15 8.314 593.15 593.15
Example (page 496)
Finally,
@418.15K: ln K = -1.9356 and K = 1.443 x 10-1
@593.15K: ln K = -5.8286 and K = 2.942x 10-3
Application of Eqs. (13.21), (13.22), and (13.24)
provides an alternative solution to this example. By
Eq. (13.21),

8,378 H 0 45,792
K 0 exp 29.366 18.473
8.314 298.15 RT0 8.314 298.15
Example(page496)
Moreover,
With these values, the following results are readily
obtained:
T/ K K0 K1 K2 K

298.15 1 29.366 1 1 29.366

418.15 1.4025 29.366 4.985x10-3 0.9860 1.443x10-1

593.15 1.9894 29.366 1.023x10-4 0.9794 2.942x10-3

Clearly, the influence of K1, is far greater than that of


K2. This is a typical result, and accounts for the fact
that the lines on Fig. 13.2 are nearly linear.
Example 13.7 (page 505)

In a laboratory investigation, acetylene is


catalytically hydrogenated to ethylene at
1120C and 1 bar. If the feed is an equimolar
mixture of acetylene and hydrogen, what is
the composition of the product stream at
equilibrium?

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